CN108987682A - It can prevent the preparation method of the Ni-based persursor material of richness of breakage of particles - Google Patents
It can prevent the preparation method of the Ni-based persursor material of richness of breakage of particles Download PDFInfo
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Abstract
The invention discloses the preparation methods that one kind can prevent the Ni-based persursor material of richness of breakage of particles, comprising the following steps: allotment reaction paste sets the targeted particle size D of presoma50=d；During carrying out preparation reaction, the real-time granularity D of reactant is generated by monitoring50, it is denoted as d1；As the d of actual measurement1Numerical value when being significantly less than d value, the size distribution Span value for generating reactant is turned down by changing process conditions, as the subsequent d for monitoring actual measurement1When numerical value is near d value, changes process conditions again and the size distribution Span value for generating reactant is turned up, so that the control of Span value is in a certain range；In the control range for keeping Span value, continue subsequent preparation reaction, until the reactant particle size growth generated, which to d value, then carries out subsequent processing, obtains rich Ni-based persursor material.The present invention can prepare the Ni-based persursor material of richness that variable grain size, high sphericity and particle do not rupture.
Description
Technical field
The invention belongs to lithium ion battery material technical field more particularly to a kind of preparation sides of positive persursor material
Method.
Background technique
Lithium ion battery has many advantages, such as having extended cycle life, is highly-safe, memory-less effect, is widely used in various
Mobile communication equipment and electric car field, and the promotion of performance of lithium ion battery is heavily dependent on lithium electricity positive electrode
The sustained improvement of performance.Commercialized lithium electricity positive electrode has cobalt acid lithium, LiMn2O4, LiFePO4 and nickle cobalt lithium manganate.In recent years
Carry out the rapid development with electric car field, more stringent requirements are proposed to lithium ion battery energy density, nickle cobalt lithium manganate
For other opposite positive electrodes, have the advantages that unit gram volume is high, the application in electric car field is gradually favored.
Nickle cobalt lithium manganate is since the ratio of nickel, cobalt, manganese is different, and the performances such as capacity, circulation, multiplying power of material are variant, Er Qiesui
The raising of nickel content, nickle cobalt lithium manganate unit gram volume can correspondingly increase, therefore, develop rich nickel-base anode material and have become
The R&D direction of lithium electricity industrial circle.
Nickle cobalt lithium manganate generally is calcined to obtain by nickel cobalt manganese hydroxide and lithium carbonate by high temperature solid-state method, therefore nickel cobalt
The performance of LiMn2O4 largely inherits the performance of nickel cobalt manganese hydroxide, develops the nickel cobalt manganese hydroxide of function admirable
It is the important prerequisite for preparing high-end nickle cobalt lithium manganate.
Nickel cobalt manganese hydroxide generally uses coprecipitation method to prepare, and utilizes nickel salt, cobalt salt, manganese salt and hydroxide, ammonia
Water forms spherical nickel cobalt manganese hydroxide under certain reaction system, but with the raising of nickel content, nickel cobalt manganese hydroxide
It is low that object is easy to appear breakage of particles, tap density, leads to high-nickel material poor circulation, the disadvantages of stability is poor.The prior art
CN105118981A uses high and low rotating speed method and controls nickelic granular precursor splintering problem when preparing nickelic presoma,
But this method is easy to appear reunion between medium grain, bulge phenomenon occurs in bulky grain, influences presoma when the slow-speed of revolution controls
Sphericity, and when preparing the nickelic presoma of big partial size, this phenomenon can be particularly evident, although sacrificing large granular spherical degree
On the basis of, it solves nickelic granular precursor splintering problem, but sphericity is poor, is unfavorable for sintering finished carry out secondary treatment, because
This still deposits biggish limitation.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Kind can prevent the preparation method of the Ni-based persursor material of richness of breakage of particles, and method of the invention is during precursor preparation
Pass through process control, so that it may prepare the Ni-based presoma material of richness that variable grain size, high sphericity and particle do not rupture
Material.
In order to solve the above technical problems, technical solution proposed by the present invention is before one kind can prevent the richness of breakage of particles Ni-based
Drive the preparation method of body material, which comprises the following steps: allotment reaction paste sets the targeted particle size of presoma
D50=d；
During the reaction paste carries out preparation reaction, monitors to generate in reaction paste by continuance test and react
The real-time granularity D of object50, it is denoted as d1；
As the d of actual measurement1Numerical value when being significantly less than d value, the size distribution of reactant will be generated by changing process conditions
Span value is turned down, so that the d of subsequent reactions actual measurement1Numerical value it is close to d；Wherein Span=(D90-D10)/D50；
As the subsequent d for monitoring actual measurement1Numerical value constantly close to d value and near d value when, changing process conditions again will
The size distribution Span value for generating reactant is turned up, so that the size distribution Span value of subsequent reactions actual measurement is controlled in certain model
It encloses；
The control range of above-mentioned Span value is kept again, continues subsequent preparation reaction, until the reactant granularity generated is long
D value is arrived greatly, then carries out subsequent processing, obtains rich Ni-based persursor material.
Above-mentioned preparation method, preferred: the concrete operations of the allotment reaction paste include:
According to the element proportion in the Ni-based persursor material of richness, mixed salt solution, sodium hydroxide solution are prepared
And ammonium hydroxide；
It is first pumped into ammonium hydroxide into reaction kettle, makes the ammonia density 8-16g/L in reaction kettle bottom liquid, then use sodium hydroxide solution
The pH of reaction kettle bottom liquid is adjusted to target ph, and reaction kettle bottom liquid is made not have the agitating paddle of reaction kettle；Again to reaction kettle
In be filled with inert gas, open stirring；Then utilize peristaltic pump by the mixed salt solution, sodium hydroxide solution and ammonia of preparation
Water is added in reaction kettle by setting flow velocity cocurrent.
Since reaction kettle revolving speed and flow are there are certain matching relationship, P (stirring)/V can play pattern and primary particle
To great influence；In addition, our experiences show that, the concentration of metal salt solution flow and ammonium hydroxide is it is also preferred that there are certain correspondences
Relationship, salt flow determine the residence time of material in reactor, have certain effect, while the flow pair of ammonium hydroxide to the control of D50
Bottom water ammonia density has a certain impact in reaction kettle.Based on this, above-mentioned preparation method is preferred: the mixed metal salt
The total concentration control of metal ion in solution is controlled in 1-2mol/L, the concentration of the sodium hydroxide solution in 6-10mol/L, institute
The concentration for stating ammonium hydroxide is controlled in 10-13mol/L；The mixed salt solution sets flow velocity as 6-12L/h, the ammonium hydroxide
Flow velocity is set as 0.4-1.2L/h (sodium hydroxide solution flow can be adjusted by pH value self-checking device).
Above-mentioned preparation method, it is preferred: the targeted particle size D50Size be set as 9 μm≤d≤16 μm；If granularity
Too small, second particle may not rupture, if granularity is excessive, can not may just better solve the rupture of nickelic presoma ball
Problem；
The d of the actual measurement1Numerical value be significantly less than d value and refer to d1< d-4 μm；
The d of the actual measurement1Numerical value constantly refer to the d of actual measurement close to d value and near d value1Numerical value move closer to and straight
To the range for falling in d-4 μm~d+4 μm.
Since the size of feed rate and reaction kettle volume determines the growth rate of particle, and the size of growth rate
Determine that Span < 1 is adjusted to span > 1 and D again50The process to become larger, therefore, above-mentioned granularity control is integrated by us
The result for adjusting and being obtained after optimizing repeatedly.
Above-mentioned preparation method, preferred: the size distribution Span value that will generate reactant, which is turned down, to be referred to and will generate
The size distribution Span value of reactant is adjusted to 1 or less；
The size distribution Span value control for surveying subsequent reactions refers in a certain range by size distribution Span value
It is maintained at and is greater than 1 and the range less than 1.4.We repeatedly studies have shown that the fine grained in reaction kettle accounts for as span < 1
Than tailing off, particle can grow up, and as Span > 1, fine grained number becomes more, reaction kettle endoparticle D50It is difficult to become larger, as charging is held
Continuous to carry out, targeted particle size can be stablized substantially, as Span > 1.4, D90Excessive or D10Too small, product is difficult qualification at this time.
Above-mentioned preparation method, it is preferred: it is described change process conditions include pH value when changing reaction, ammonia density value,
At least two parameters in ammonium hydroxide feed flow rate value, metal salt solution feed flow rate value；But more preferably change pH when reaction
Value and ammonia density value, or change ammonium hydroxide feed flow rate value and metal salt solution feed flow rate value；
The size distribution Span value for generating reactant, which is turned down, to be realized by changing following process conditions: will be reacted
When pH control smaller than target ph initially set by least 0.2, ammonia density when reacting is controlled than initially set
At least more 2g/L of ammonia density in reaction kettle bottom liquid, by when reacting metal salt solution feed flow rate value control initially set into
1.1~1.2 times of stream speed；
It is described again change process conditions will generate reactant size distribution Span value height-regulating refer to by above-mentioned change with
Process conditions afterwards are restored within the scope of process parameter value initially set, particularly preferred, such as by the pH tune of reaction system
It saves to 12~12.4, ammonia density value is adjusted to 8~12g/L, metal salt solution flow velocity is adjusted to 6~10L/h, by ammonia aqua stream
Amount control is in 0.4~1.0L/h.
Above-mentioned preparation method, preferred: the Ni-based persursor material of richness refers to nickel cobalt manganese hydroxide precursor, institute
The chemical formula for stating nickel cobalt manganese hydroxide precursor is NixCoyMn1-x-y(OH)2, wherein 0.6≤x≤0.9,0.05≤y≤0.2
(persursor material of this type is particularly easy to rupture)；Mesh in the Ni-based persursor material preparation reaction process of richness
Mark pH value is set as 11.6~12.4.The target ph determines that method preferably passes through following formula pH=6.65+0.51gS-
0.51gC (S satiety degree, C=C Ni-1/6C NH3) realize.
Above-mentioned preparation method, preferred: the stirring frequency of the reaction kettle in the preparation reaction process is 40~50Hz,
Controlling reaction temperature is 50 DEG C~60 DEG C.The height of reaction temperature is to nucleation rate (generating thin core can be excessive) and growth rate
(i.e. thin core becomes larger) can be had an impact, if temperature is lower than 50 DEG C, generally generating thin core can be excessive, and temperature is general raw higher than 60 DEG C
Length is too fast, and temperature is excessively high, and energy consumption also can be bigger than normal.
Above-mentioned preparation method, it is preferred: the subsequent processing the following steps are included:
Obtained qualified reaction product slurry after the reaction was completed, is transported to aging reactor and is aged by preparation；Ageing terminates
After carry out filters pressing, while the sodium hydroxide solution that mass fraction is 2.4%~3.2% is added and is washed, while controlling lye
Temperature 60 C~70 DEG C；After alkali liquid washing again use pure water, until wash water pH < 9.5, then by the complete material of filters pressing into
Row drying, is sieved, and saves.
The technical solution of aforementioned present invention is based primarily upon following principle:
1. the problem of our long-term experimental studies show breakage of particles is that the stress inside when fine grained becomes larger is excessive
Cause, the speed for indicating that fine grained is reunited if growth is too fast is big, and fine grain extruding degree becomes larger, then secondary ball particle holds
Easy to crack, it is the shock between particle inside reaction kettle that on the other hand there is also certain to be associated with the shock between particle, if
Particle is small, then large specific surface area, and stress is small between particle, and if fruit granule becomes larger, then specific surface becomes smaller, and impact force becomes larger between particle,
More easily rupture, and adjusting span value is means, core is to adjust the size relation of reaction system nucleation and growth rate, simultaneously
Span value is related to D90、D10、D50Size, namely be related to the accounting situation of variable grain, indirect reaction size particles and at
The relationship of core and growth rate.By optimizing the reaction process of presoma, nucleation rate and the life of presoma reaction process are adjusted
The size relation of long rate regulates and controls the size particles collocation during reaction system, makes particle using the size of surveyed Span value
Between friction be effectively controlled with shock, to solve nickelic granular precursor splintering problem；
2. the present invention is with targeted particle size D50Specific node value be boundary, pass through and adjust raw material flow rate, reaction pH and ammonia value
Deng, and then controlled by Span value, make reaction in two control systems, so that presoma be made to obtain during nucleation and growth
Effective coordination is arrived.
Compared with the prior art, the advantages of the present invention are as follows:
1. for existing regulation revolving speed solves nickelic ball particle disruption method, method invariablenes turning speed of the invention,
Presoma can be effectively prevented and bulge phenomenon occur, improve the dispersibility of reaction system, keep the spherical shape of high Ni-based presoma
Degree；
2. big in reaction system by adjusting the present invention is especially suitable for the rich Ni-based presoma of medium partial size bigger than normal is prepared
Small accounting situation, so that the shock between particle and between particle and reaction kettle inner wall is weakened, to obtain granularity
It is evenly distributed, the Ni-based presoma of richness that sphericity is perfect.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the Ni that the embodiment of the present invention 1 is prepared0.8Co0.1Mn0.1(OH)2Particle showing under 10000 times of Electronic Speculum
It is intended to.
Fig. 2 is the Ni that the embodiment of the present invention 1 is prepared0.8Co0.1Mn0.1(OH)2Signal of the particle under 5000 times of Electronic Speculum
Figure.
Fig. 3 is the Ni that comparative example 1 obtains0.8Co0.1Mn0.1(OH)2Schematic diagram of the particle under 10000 times of Electronic Speculum.
Fig. 4 is the Ni that comparative example 1 obtains0.8Co0.1Mn0.1(OH)2Schematic diagram of the particle under 5000 times of Electronic Speculum.
Fig. 5 is the Ni that embodiment 2 obtains0.85Co0.1Mn0.05(OH)2Schematic diagram of the particle under 10000 times of Electronic Speculum.
Fig. 6 is the Ni that embodiment 2 obtains0.85Co0.1Mn0.05(OH)2Schematic diagram of the particle under 5000 times of Electronic Speculum.
Fig. 7 is the Ni that comparative example 2 obtains0.8Co0.1Mn0.1(OH)2Particle schematic diagram under 10000 times of Electronic Speculum.
Fig. 8 is the Ni that comparative example 2 obtains0.8Co0.1Mn0.1(OH)2Particle schematic diagram under 5000 times of Electronic Speculum.
Specific embodiment
A kind of specific embodiment of the invention is given below.
A kind of Ni-based persursor material Ni of richness preventing breakage of particlesxCoyMn1-x-y(OH)2Preparation method, it is rich Ni-based
Persursor material NixCoyMn1-x-y(OH)2D50Size be set as 9 μm≤d≤16 μm, which specifically includes following
Step:
(1) according to rich Ni-based persursor material NixCoyMn1-x-y(OH)2Middle metal ion ratio prepares the mixed of 1-2mol/L
Close metal salt solution, the sodium hydroxide solution of 6-10mol/L and the ammonium hydroxide of 10-13mol/L；
(2) it is pumped into ammonium hydroxide into reaction kettle, makes the ammonia density target ammonia density 8-16g/L in reaction kettle bottom liquid, then
The pH of reaction kettle bottom liquid is adjusted to target ph=11.6-12 with sodium hydroxide solution, and bottom liquid is made not have stirring for reaction kettle
Mix paddle；
(3) it being filled with nitrogen into reaction kettle, opens stirring, stirring frequency 40-50Hz, control reaction temperature is 50 DEG C-
60℃；
(4) mixed salt solution, sodium hydroxide solution, ammonium hydroxide cocurrent are added in reaction kettle using peristaltic pump, if
The flow velocity of mixed salt solution is set in 6-12L/h, ammonium hydroxide flow control automatically controls reaction kettle in 0.4-1.2L/h, by pH
PH, be in pH within the scope of above-mentioned pH, flux of alkaline liquor automatic adjustment；
(5) with the lasting progress of charging, fine grained is gradually grown up, fine grained sphericity gradual perfection, when subsequent monitoring
The reaction product granularity d into slurry1When < d-4 μm, the size distribution for making to generate reactant is adjusted by changing process conditions
Span value < 1；Specifically by pH control when reacting smaller than target ph initially set by least 0.2, by ammonia when reacting
Concentration control is 2g/L at least more than the ammonia density in reaction kettle bottom liquid initially set, by the charging of reaction raw materials when reacting
Flow control is in initial 1.1~1.2 times for setting feed flow rate；
(6) as feed for duration carries out, as reaction product granularity d in slurry1When > d-4 μm, by the pH of reaction system
12-12.4 is adjusted, the flow velocity of ammonia density value regulation to 8-12g/L, mixed salt solution is adjusted to 7.2-10L/h, ammonium hydroxide
Flow control makes the size distribution Span value for generating reactant in 1.1- in 0.4-1.0L/h, by changing process conditions adjusting
1.4；
(7) as reaction carries out, presoma particle size growth to target D50Value；When detecting second particle aggregation size ruler
When very little d is 9-16 μm, qualified material is collected, overflow stream enters aging reactor and is aged；
(8) after being aged, filters pressing is carried out using sheet frame press machine, while it is 2.4%-3.2%'s that mass fraction, which is added,
Sodium hydroxide solution is washed, while controlling 60 DEG C -70 DEG C of alkali liquid temperature；
(9) pure water is used after alkali liquid washing again, until wash water pH < 9.5, then carries out 110 DEG C for the complete material of filters pressing
Drying；
(10) material dried carries out 325 mesh screen screenings, is sealed.
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of Ni-based persursor material Ni of richness for preventing breakage of particles of the invention0.8Co0.1Mn0.1(OH)2Preparation side
Method, rich Ni-based persursor material Ni0.8Co0.1Mn0.1(OH)2D50Size be set as 10 ± 0.5 μm, the preparation method is specific
The following steps are included:
(1) according to rich Ni-based persursor material molecular formula Ni0.8Co0.1Mn0.1(OH)2Middle metal ion ratio prepares 2mol/
The ammonium hydroxide of the mixed salt solution of L, the sodium hydroxide solution of 10mol/L and 13mol/L；
(2) ammonium hydroxide of 13mol/1 is pumped into reaction kettle, the target ammonia density for setting the ammonia density of reaction kettle bottom liquid
12-13g/L, then with the sodium hydroxide solution of 10mol/L by the pH of reaction kettle bottom liquid adjust the target ph to setting=
11.8, and bottom liquid is made not have the stirring of reaction kettle；For target ammonia density CNH3=1/6CM, CMIndicate salinity, pH=6.65+
0.51gS-0.51gC；
(3) it is filled with nitrogen into reaction kettle, opens stirring, stirring frequency 50Hz, control reaction temperature is 60 DEG C；
(4) mixed salt solution, sodium hydroxide solution, ammonium hydroxide cocurrent are added in reaction kettle using peristaltic pump, if
The flow velocity of mixed salt solution is set in 12L/h, ammonium hydroxide flow control automatically controls the pH of reaction kettle by pH in 1.2L/h,
PH is set to be in target ph；
(5) with the lasting progress of charging, fine grained is gradually grown up, fine grained sphericity gradual perfection, is overflow from reaction kettle
Head piece utilizes small beaker splicing, behind in small beaker slurry ultrasound 1 minute, checks slurry using 2000 particle size analyzer of Malvern
Granularity, using the above method, every two hour tests a slurry granularity, when detecting that reaction product granularity is less than in slurry
At 6 μm, by changing process conditions, specifically pH control when reacting is existed ammonia density control when reacting 11.6
15g/L surveys reaction by the feed flow rate control of reaction raw materials when reacting at 1.2 times of initially setting feed flow rate
Size distribution Span value is adjusted to span < 1；
(6) as feed for duration carries out, small beaker splicing is utilized from reaction kettle overflow port, by slurry ultrasound 1 in small beaker
After minute, slurry granularity is checked using 2000 particle size analyzer of Malvern, using the above method, the primary slurry of every two hour test
Material granularity, when detecting that reaction product granularity is greater than 6 μm in slurry, by reaction system pH adjusting to 12, ammonia density value tune
10-11g/L is controlled, the flow velocity for closing metal salt solution is adjusted to 10L/h, and ammonium hydroxide flow control is in 1L/h, by changing technique item
Part, which is adjusted, makes the size distribution Span value for generating reactant in 1.1-1.4；
(7) as reaction carries out, presoma particle size growth to target value D50=10 ± 0.5 μm, collect qualified material, overflow material
Aging reactor is flowed into be aged；
(8) after being aged, filters pressing is carried out using sheet frame press machine, while the hydroxide that mass fraction is 3.2% is added
Sodium solution is washed, while controlling 60-70 DEG C of alkali liquid temperature；
(9) pure water is used after alkali liquid washing again, until wash water pH < 9.5, then carries out 110 DEG C for the complete material of filters pressing
Drying；
(10) material dried carries out 325 mesh screen screenings, is sealed.
The electromicroscopic photograph for the product that the present embodiment is prepared is as shown in Figure 1 and Figure 2, as seen from the figure, secondary bulky grain and two
Secondary little particle sphericity is perfect, and primary particle arrangement is uniformly, using rich nickel presoma second particle manufactured in the present embodiment without
Slight crack.
Comparative example 1:
A kind of Ni-based persursor material Ni of richness for preventing breakage of particles of the invention0.8Co0.1Mn0.1(OH)2Preparation side
Method, rich Ni-based persursor material Ni0.8Co0.1Mn0.1(OH)2D50Size be set as 10 ± 0.5 μm, the preparation method is specific
The following steps are included:
(1) according to rich Ni-based persursor material molecular formula Ni0.8Co0.1Mn0.1(OH)2Middle metal ion ratio prepares 2mol/
The ammonium hydroxide of the mixed salt solution of L, the sodium hydroxide solution of 10mol/L and 13mol/L；
(2) ammonium hydroxide of 13mol/1 is pumped into reaction kettle, the target ammonia density for setting the ammonia density of reaction kettle bottom liquid
12-13g/L, then with the sodium hydroxide solution of 10mol/L by the pH of reaction kettle bottom liquid adjust the target ph to setting=
11.8, and bottom liquid is made not have the agitating paddle of reaction kettle；
(3) it is filled with nitrogen into reaction kettle, opens stirring, stirring frequency 50Hz, control reaction temperature is 60 DEG C；
(4) mixed salt solution, sodium hydroxide solution, ammonium hydroxide cocurrent are added in reaction kettle using peristaltic pump, if
The flow velocity of mixed salt solution is set in 12L/h, ammonium hydroxide flow control automatically controls the pH of reaction kettle by pH in 1.2L/h,
PH is set to be in target ph；
(5) with the lasting progress of charging, fine grained is gradually grown up, fine grained sphericity gradual perfection, when from reaction kettle
Overflow port utilizes small beaker splicing, behind in small beaker slurry ultrasound 1 minute, is starched using 2000 particle size analyzer inspection of Malvern
Material granularity, using the above method, every two hour tests a slurry granularity, detects that reaction product granularity is less than in slurry
At 6 μm, by changing process conditions, specifically pH control when reacting is existed ammonia density control when reacting 11.6
15g/L surveys reaction by the feed flow rate control of reaction raw materials when reacting at 1.2 times of initially setting feed flow rate
Size distribution Span value is adjusted to span < 1；
(6) as feed for duration carries out, when detecting that reaction product granularity is greater than 6 μm in slurry, by reaction system
PH is adjusted to 12, and ammonia density value regulation to 10-11g/L, the flow velocity for closing metal salt solution is adjusted to 10L/h, ammonium hydroxide flow control
In 1L/h, make the size distribution Span value for generating reactant in 1.1-1.4 by changing process conditions adjusting；
(7) as reaction carries out, presoma particle size growth to target value D50=10 ± 0.5 μm, collect qualified material, overflow material
Aging reactor is flowed into be aged；
(8) after being aged, filters pressing is carried out using sheet frame press machine, while the hydroxide that mass fraction is 3.2% is added
Sodium solution is washed, while controlling 60-70 DEG C of alkali liquid temperature；
(9) pure water is used after alkali liquid washing again, until wash water pH < 9.5, then carries out 110 DEG C for the complete material of filters pressing
Drying；
(10) material dried carries out 325 mesh screen screenings, is sealed.
The electromicroscopic photograph for the product that the present embodiment is prepared is as shown in Figure 3, Figure 4.The present embodiment is using in background technique
The method mentioned prevents nickelic granular precursor from rupturing, but can be seen that secondary bulky grain rouses from electromicroscopic photograph Fig. 3, Fig. 4
Packet phenomenon, sphericity is poor, for embodiment 1, although second particle does not also rupture, occurs bulge between particle
Phenomenon influences sphericity.
Embodiment 2
A kind of Ni-based persursor material Ni of richness0.85Co0.1Mn0.05(OH)2Preparation method, rich Ni-based persursor material
Ni0.85Co0.1Mn0.05(OH)2D50Size be set as 10 ± 0.5 μm, the preparation method specifically includes the following steps:
(1) according to rich Ni-based persursor material molecular formula Ni0.85Co0.1Mn0.05(OH)2Middle metal ion ratio is prepared
The ammonium hydroxide of the mixed salt solution of 2mol/L, the sodium hydroxide solution of 10mol/L and 13mol/L；
(2) ammonium hydroxide of 13mol/L is pumped into reaction kettle, the target ammonia density for setting the ammonia density of reaction kettle bottom liquid
11-12g/L, then with the sodium hydroxide solution of 10mol/L by the pH of reaction kettle bottom liquid adjust the target ph to setting=
11.9, and bottom liquid is made not have the agitating paddle of reaction kettle；
(3) it is filled with nitrogen into reaction kettle, opens stirring, stirring frequency 50Hz, control reaction temperature is 55 DEG C；
(4) mixed salt solution, sodium hydroxide solution, ammonium hydroxide cocurrent are added in reaction kettle using peristaltic pump, if
The flow velocity of mixed salt solution is set in 12L/h, ammonium hydroxide flow control automatically controls the pH of reaction kettle by pH in 1.2L/h,
PH is set to be in target ph；
(5) with the lasting progress of charging, fine grained is gradually grown up, fine grained sphericity gradual perfection, when from reaction kettle
Overflow port utilizes small beaker splicing, behind in small beaker slurry ultrasound 1 minute, is starched using 2000 particle size analyzer inspection of Malvern
Material granularity, using the above method, every two hour tests a slurry granularity, detects that reaction product granularity is less than in slurry
At 6 μm, by changing process conditions, specifically pH control when reacting is existed ammonia density control when reacting 11.6
15g/L surveys reaction by the feed flow rate control of reaction raw materials when reacting at 1.2 times of initially setting feed flow rate
Size distribution Span value is adjusted to span < 1；
(6) as feed for duration carries out, when detecting that reaction product granularity is greater than 6 μm in slurry, by reaction system
PH is adjusted to 12, and ammonia density value regulation to 10-11g/L, the flow velocity for closing metal salt solution is adjusted to 10L/h, ammonium hydroxide flow control
In 1L/h, make the size distribution Span value for generating reactant in 1.1-1.4 by changing process conditions adjusting；
(7) as reaction carries out, presoma particle size growth to target value D50=10 ± 0.5 μm, collect qualified material, overflow material
Aging reactor is flowed into be aged；
(8) after being aged, filters pressing is carried out using sheet frame press machine, while the hydroxide that mass fraction is 3.2% is added
Sodium solution is washed, while controlling 60-70 DEG C of alkali liquid temperature；
(9) pure water is used after alkali liquid washing again, until wash water pH < 9.5, then carries out 110 DEG C for the complete material of filters pressing
Drying；
(10) material dried carries out 325 mesh screen screenings, is sealed.
The electromicroscopic photograph for the product that the present embodiment is prepared is as shown in Figure 5, Figure 6, as seen from the figure, secondary bulky grain and two
Secondary little particle sphericity is perfect, and primary particle arrangement is uniformly, using rich nickel presoma second particle manufactured in the present embodiment without
Slight crack.
Comparative example 2
A kind of Ni-based persursor material Ni of richness0.8Co0.1Mn0.1(OH)2Preparation method, rich Ni-based persursor material
Ni0.8Co0.1Mn0.1(OH)2D50Size be set as 10 μm, the preparation method specifically includes the following steps:
(1) according to rich Ni-based persursor material molecular formula Ni0.8Co0.1Mn0.1(OH)2Middle metal ion ratio prepares 2mol/
The ammonium hydroxide of the mixed salt solution of L, the sodium hydroxide solution of 10mol/L and 13mol/L；
(2) ammonium hydroxide of 13mol/l is pumped into reaction kettle, the target ammonia density for setting the ammonia density of reaction kettle bottom liquid
12-13g/L, then with the sodium hydroxide solution of 10mol/L by the pH of reaction kettle bottom liquid adjust the target ph to setting=
11.8, and bottom liquid is made not have the agitating paddle of reaction kettle；
(3) it is filled with nitrogen into reaction kettle, opens stirring, stirring frequency 50Hz, control reaction temperature is 60 DEG C；
(4) mixed salt solution, sodium hydroxide solution, ammonium hydroxide cocurrent are added in reaction kettle using peristaltic pump, if
The flow velocity of mixed salt solution is set in 12L/h, ammonium hydroxide flow control automatically controls the pH of reaction kettle by pH in 1.2L/h,
PH is set to be in target ph；
(5) with the lasting progress of charging, fine grained is gradually grown up, fine grained sphericity gradual perfection, presoma granularity
It grows up to target value D50=10 ± 0.5 μm, qualified material is collected, overflow stream enters aging reactor and is aged；
(6) after being aged, filters pressing is carried out using sheet frame press machine, while the hydroxide that mass fraction is 3.2% is added
Sodium solution is washed, while controlling 60 DEG C -70 DEG C of alkali liquid temperature；
(7) pure water is used after alkali liquid washing again, until wash water pH < 9.5, then carries out 110 DEG C for the complete material of filters pressing
Drying；
(8) material dried carries out 325 mesh screen screenings, is sealed.
The electromicroscopic photograph for the product that this comparative example 2 is prepared is as shown in Figure 7, Figure 8.It can be seen that from Fig. 7, Fig. 8 secondary
Large granular spherical degree is preferable, but apparent slight crack occurs in secondary ball, and size distribution is concentrated, and no fine grained occurs.
Claims (10)
1. the preparation method that one kind can prevent the Ni-based persursor material of richness of breakage of particles, which comprises the following steps:
Reaction paste is deployed, the targeted particle size D of presoma is set50=d；
During the reaction paste carries out preparation reaction, is monitored by continuance test and generate reactant in reaction paste
Real-time granularity D50, it is denoted as d1；
As the d of actual measurement1Numerical value when being significantly less than d value, the size distribution Span value of reactant will be generated by changing process conditions
It turns down, so that the d of subsequent reactions actual measurement1Numerical value it is close to d, wherein Span=(D90-D10)/D50；
As the subsequent d for monitoring actual measurement1Numerical value constantly close to d value and near d value when, changing process conditions again will generate
The size distribution Span value of reactant is turned up, so that the size distribution Span value of subsequent reactions actual measurement is controlled in a certain range；
It keeps the control range of above-mentioned Span value again, continues subsequent preparation reaction, until the reactant particle size growth of generation is to d
Value, then carries out subsequent processing, obtains rich Ni-based persursor material.
2. preparation method according to claim 1, it is characterised in that: it is described allotment reaction paste concrete operations include:
According to the element proportion in the Ni-based persursor material of richness, mixed salt solution, sodium hydroxide solution and ammonia are prepared
Water；
It is first pumped into ammonium hydroxide into reaction kettle, makes the ammonia density 8-16g/L in reaction kettle bottom liquid, then will be anti-with sodium hydroxide solution
It answers the pH of kettle base solution to adjust to target ph, and reaction kettle bottom liquid is made not have the agitating paddle of reaction kettle；It is filled again into reaction kettle
Enter inert gas, opens stirring；Then the mixed salt solution, sodium hydroxide solution and ammonium hydroxide of preparation are pressed using peristaltic pump
Setting flow velocity cocurrent is added in reaction kettle.
3. preparation method according to claim 2, it is characterised in that: metal ion is total in the mixed salt solution
Concentration control is in 1-2mol/L, and in 6-10mol/L, the concentration control of the ammonium hydroxide exists for the concentration control of the sodium hydroxide solution
10-13mol/L；The mixed salt solution sets flow velocity as 6-12L/h, and the ammonium hydroxide sets flow velocity as 0.4-
1.2L/h。
4. preparation method according to claim 1 or 2 or 3, it is characterised in that: the targeted particle size D50Size be set as
9μm≤d≤16μm；
The d of the actual measurement1Numerical value be significantly less than d value and refer to d1< d-4 μm；
The d of the actual measurement1Numerical value constantly refer to the d of actual measurement close to d value and near d value1Numerical value move closer to and until fall
In d-4 μm~d+4 μm of range.
5. preparation method according to claim 1 or 2 or 3, it is characterised in that: the size distribution that reactant will be generated
Span value, which is turned down, to be referred to the size distribution Span value for generating reactant being adjusted to 1 or less；
The size distribution Span value control for surveying subsequent reactions refers in a certain range keeps size distribution Span value
It is being greater than 1 and the range less than 1.4.
6. preparation method according to claim 1 or 2 or 3, it is characterised in that: the change process conditions include changing instead
Seasonable pH value, ammonia density value, ammonium hydroxide feed flow rate value, at least two parameters in metal salt solution feed flow rate value；
The size distribution Span value for generating reactant, which is turned down, to be realized by changing following process conditions: when by reacting
PH control controls ammonia density when reacting than reaction initially set smaller than target ph initially set by least 0.2
At least more 2g/L of ammonia density in kettle base solution, by metal salt solution feed flow rate value control when reacting in initially setting feeding flow
1.1~1.2 times of speed；
The size distribution Span value height-regulating that the process conditions of change again will generate reactant refers to above-mentioned change is later
Process conditions are restored within the scope of process parameter value initially set.
7. preparation method according to claim 6, it is characterised in that: described to be restored to process parameter value model initially set
It encloses and refers to: the pH of reaction system being adjusted to 12~12.4, ammonia density value is adjusted to 8~12g/L, by metal salt solution flow velocity
It adjusts to 6~10L/h, by ammonium hydroxide flow control in 0.4~1.0L/h.
8. preparation method according to claim 1 or 2 or 3, it is characterised in that: the Ni-based persursor material of richness refers to nickel
Cobalt manganese hydroxide precursor, the chemical formula of the nickel cobalt manganese hydroxide precursor are NixCoyMn1-x-y(OH)2, wherein 0.6
≤ x≤0.9,0.05≤y≤0.2；Target ph in the Ni-based persursor material preparation reaction process of richness is set as 11.6
~12.4.
9. preparation method according to claim 1 or 2 or 3, it is characterised in that: the reaction kettle in the preparation reaction process
Stirring frequency be 40~50Hz, control reaction temperature be 50 DEG C~60 DEG C.
10. preparation method according to claim 1 or 2 or 3, it is characterised in that: the subsequent processing includes following step
It is rapid:
Obtained qualified reaction product slurry after the reaction was completed, is transported to aging reactor and is aged by preparation；Ageing terminates laggard
Row filters pressing, while the sodium hydroxide solution that mass fraction is 2.4%~3.2% is added and is washed, while controlling alkali liquid temperature
60 DEG C~70 DEG C；Pure water is used after alkali liquid washing again, until the pH < 9.5 of wash water, then dries the complete material of filters pressing
It is dry, it is sieved, saves.
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